Synthesis and characterization of electrochemically polymerized metal-free, nickel and zinc containing phthalocyanine derivatives

Yavuz, Arzu
In the first part of this study, 4-(2,5-di-2-thiophen-2-yl-pyrrol-1-yl)-phthalonitrile (SNS-PN) was synthesized by utilizing 1,4-di(2-thienyl)-1,4- butadione (SOOS) and 4-aminophthalonitrile via Knorr-Paal Reaction. Nuclear magnetic resonance (1H NMR and 13C NMR) and fourier transform infrared (FTIR) spectroscopies were utilized for the characterization of this compound. SNS-PN monomer was then electrochemically polymerized in acetonitrile/0.2 M LiClO4 solvent/electrolyte couple. Characterizations of the resulting polymer P(SNS-PN) were carried out by cyclic voltammetry (CV), UV–vis and FTIR spectroscopic techniques. Spectroelectrochemical studies revealed that P(SNS-PN) has an electronic band gap of 2.5 eV and exhibits electrochromic behaviour. The switching ability of polymer was also monitored. It was also found that P(SNS-PN) was fluorescent and its fluorescence intensity enhanced in the presence of cations. In the second part, novel tetrakis (4-(2,5-di-2-thiophen-2-yl-pyrrol-1-yl)) substituted metal-free (H2Pc-SNS), zinc (ZnPc-SNS) and nickel phthalocyanine (NiPc-SNS) complexes were synthesized and characterized by elemental analysis, FTIR and UV-Vis spectroscopies. The solution redox properties of these complexes were also studied by using CV and differential pulse voltammetry. All of the complexes showed two reversible reduction peaks having ligand-based character and one irreversible oxidation peak. Also, the electrochemical polymerization of these complexes was performed in dichloromethane/tetrabutylammonium perchlorate solvent/electrolyte couple. Resulting polymer films were characterized by UV–vis and FTIR spectroscopic techniques and their electrochemical behaviors were investigated utilizing CV. In-situ spectroelectrochemical investigations revealed that all the polymer films could be reversibly cycled and exhibit electrochromic behavior. Furthermore, the band gap of P(H2Pc-SNS), P(ZnPc-SNS) and P(NiPc-SNS) were calculated as 2.38 eV, 2.25 eV and 2.69 eV, respectively. Moreover, the fluorescence property of the P(ZnPc-SNS) was investigated in dimethyl sulfoxide and toluene.


Synthesis and Stimuli-Responsive Properties of Metallo-Supramolecular Phosphazene Polymers Based on Terpyridine Metal Complexes
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Kıralp, Senem; Kıralp, Senem; Department of Chemistry (2004)
A new thiophene derivative containing menthyl group (MM) was synthesized and polymerized via chemical and electrochemical methods. Polymers obtained and MM itself were used to synthesize copolymers with pyrrole under conditions of constant potential electrolysis. Cyclic Voltammetry, thermal analysis and scanning electron microscopy analyses were performed for the characterization of samples. Immobilization of invertase and polyphenol oxidase enzymes was performed in the matrices obtained via copolymerizatio...
Electrochemical synthesis of new conjugated polymers based on carbazole and furan units
Oguzturk, H. Esra; TİRKEŞ, SEHA; Önal, Ahmet Muhtar (2015-08-01)
In this study, synthesis of four new monomers; 3,6-di(2-furyl)-9H-carbazole (M1), 3,6-di(2-furyl)-9-ethyl-carbazole (M2), 2,7-di(2-furyl)-9-H-carbazole (M3), 2,7-di(2-furyl)-9-(tridecan-7-yl)-9H-carbazole (M4), was achieved via Stifle cross-coupling reaction. The monomers were electrochemically polymerized, via repetitive cycling in acetonitrile-tetrabutylammonium hexafluorophosphate electrolytic medium. Optical and electrochemical properties of the monomers and their corresponding polymers were investigate...
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Öztürk, Elif; Alyürük, Kemal; Department of Polymer Science and Technology (2006)
The synthesis of high molecular weight copolymer of carbon disulphide (CS2) and propylene oxide (PO) has not reported in literature. In the present work, zinc isopropyl xanthate (Zn(Xt)2) was used as catalyst for the copolymerisation of PO and CS2 into high copolymer. However, the product can be fractionated into high and low molecular weight components. High molecular weight copolymer was rubbery products, but low molecular weight copolymers were oily products containing cyclic dithiocarbonates. Copolymers...
Citation Formats
A. Yavuz, “Synthesis and characterization of electrochemically polymerized metal-free, nickel and zinc containing phthalocyanine derivatives,” Ph.D. - Doctoral Program, Middle East Technical University, 2009.